Perfume compositions containing ethyl 2,4-dioxohexanoate

ABSTRACT

The present invention comprises perfume compositions containing ethyl 2,4-dioxohexanoate.

United States Patent 1 Hajos et al.

[ PERFUME COMPOSITIONS CONTAINING ETHYL 2,4-DIOXOHEXANOATE [75]Inventors: Zoltan G. Hajos, Upper Montclair;

David R. Parrish, Glen Ridge, both Sept. 18, 1973 3,240,710 3/1966Schiltz 252/106 3,240,711 3/1966 Wittwer 252/106 FOREIGN PATENTS ORAPPLICATIONS 709,435 8/1941 Germany 424/311 OTHER PUBLICATIONS ChemicalAbstracts" Vol. 53 (1959) 4309.

Primary Examiner-Albert T. Meyers Assistant Examiner-Frederick E.Waddell Attorney-Samuel L. Welt, Jon S. Saxe, Bernard S. Leon, William1-1. Epstein and George M. Gould [57] ABSTRACT The present inventioncomprises perfume compositions containing ethyl 2,4-dioxohexanoate.

3 Claims, No Drawings PERFUME COMPOSITIONS CONTAINING ETI'IYL2,4-DIOXOI-IEXANOATE This invention relates to ethyl 2,4-dioxohexanoateas a component of perfume and flavored compositions i.e., as anolfactory and flavoring ingredient.

In particular, the present invention comprises the discovery that ethyl2,4-dioxohexanoate has a high odor value and desirable blendingproperties so as to be useful in perfume compositions. This inventionalso includes the discovery that ethyl 2,4-dioxohexanoate has a flavorvalue for use in flavored compositions.

The application of odiferous principles to commercial compositions likesoaps, cosmetics, creams, powders, and lotions involves a multitude ofcomplex problems. For example, soaps having unpleasant and sometimesoffensive odors cannot be successfully marketed without counteractingsuch undesirable characteristics. The magnitude of this problem isespecially great since soaps are an inexpensive commodity and cannotjustify the use of precious odorants. Accordingly, a major considerationin the selection of an olfactory ingredient is its economical coverageover the products objectionable character.

To be useful as an olfactory ingredient, a compound must be fragrant andas pleasant as possible, yet not interfere with the purpose for whichthe final product is intended by significantly affecting factors likesolubility, toxicity, color, etc. For example, soap incorporat-,

ing'an olfactory ingredient should desirably result in a finishedproduct having a uniform fragrance, high odor stability and effectivecoverage for the unpleasant odor.

SUMMARY OF THE INVENTION DESCRIPTION OF THE PREFERRED EMBODIMENT Theperfume compositions comprising the present invention provide pleasingodors which can be characterized as burnt caramel, opopanax, Cassiaabsolute, Genet absolute, Tuberose absolute and butterscotch.

As a compound reminiscent of such odors, ethyl 2,4-

' dioxohexanoate is valuable for use in perfumery, especially since thecompound can also be blended with other fragrances to obtain perfumecompositions which have widely varying odor characteristics. For examplean olfactory effective amount of ethyl 2,4- dioxohexanoate can beincorporated into any of several perfume bases to produce perfumecompositions such as cosmetics, soaps, lotions, aerosols, creams,powders and the like. As used herein, the term perfume bases comprehendsmaterials into which the fragrant ethyl 2,4-dioxohexanoate compound isadded; and the term I olfactory effective amount denotes that amount ofethyl 2,4-dioxohexanoate which is added to a perfume base to produce aperfume composition having a pleasing fragrance.

Suitable perfume bases include bubble bath, hair dressing, detergents,bar soaps, lotions, deodorants, sachets, cold creams and the like. Ofcourse, the chemical composition of each perfume base varies. Forexample, a perfume base such as bubble bath can comprise sodiumsesquicarbonate and magnesium carbonate; deodorant dusting powder cancomprise talc, hexachlorophene and magnesium carbonate, and after shavelotion can comprise denatured 95 percent ethyl alcohol, hexachloropheneand diethylene glycol, monoethyl ether. These or any other perfume basecan then be converted to a perfume composition by the addition theretoof an olfactory effective amount of ethyl 2,4-dioxohexanoate.

The compound, which is an oily liquid at room temperature, can beincorporated into any of several perfume bases in two basic ways.Firstly, it can be added directly to a perfume base or; secondly, it canbe dissolved in an alcoholic or hydro-alcoholic solution. As usedherein, the term solution comprehends colognes, extracts, toilet waters,after shave lotions and the like. Desirably the alcohol used in thesesolutions is denatured 95 percent ethyl alcohol wherein the denaturantis either l) diethylpthalate (e.g., for perfume extracts) or (2) brucinesulfate and tert. butyl alcohol (e.g., for colognes, toilet waters,etc.). The alcohols used are of two types with a fixative and without afixative. Fixatives (e.g., pentadecanolide, l5- hydroxypentadecanoiceacid lactone) are generally added to perfumery alcohols in order todepress the rawness of the alcohol odor and to hasten the maturing ofthe olfactory ingredient in solution.

The compound can also be mixed with other olfactory ingredients toproduce perfume compositions having a variety of pleasing odors. Forexample, ethyl 2,4 dioxohexanoate can be mixed with methyl N-3,7-dirnethyl-7-hydroxyoctyliden-anthranilate, linalyl acetate coeur,linalyl phenal acetate, benzyl acetate, etc. Where mixed with otherolfactory ingredients, the resulting compositions can have odors like,e.g., Cassia Absolute; Tuberose Absolute and Genet Absolute.

Irrespective of whether the alcohol is fixed, the resulting solution ofthe olfactory ingredient is aged and then chilled. The solution isdesirably aged for at least 24 hours and chilled for about 1 2 hours inthe same container which is used for preparing the solution. A solutionof deodorant colognes should preferably be aged longer, i.e., about 10days.

The concentration of the olfactory ingredient, namely, ethyl2,4-dioxohexanoate, varies with the particular kind of solution. Forexample, a perfume extract can comprise an alcohol and from about 12percent to about 25 percent of the olfactory ingredient; and a toiletwater can comprise a hydro-alcoholic solution and from about 6 to about8 percent of the compound in from about to about percent alcohol.Similarly, a cologne can comprise up to about 5 percent of the olfactoryingredient in from about 75 to about 85 percent alcohol.

All solutions are generally made on weightzvolume basis except cosmeticsolutions (e.g., after shave lotions, deodorant colognes, etc., whichare generally made on a weightzweight basis. In the former case theolfactory ingredient is added by weight and the solvent is added on asufficient quantity (q.s.) basis. Where the solution is hydro-alcholic,the alcohol is computed as a percentage of the total volume and is addedby volume to the established weight of the compound.

Incorporation of the olfactory ingredient into a perfume base iseffected by manual stirring. Certain perfume compositions such as talcshould, however, be preferably prepared with the aid of a power blender.Regardless of the blending means, sufficient mixing is necessary inorder to ensure a thoroughly homogenous distribution of the olfactoryingredient into the perfume base.

Good odorant results are obtained when the olfactory effective amount ofethyl 2,4-dioxohexanoate is up to about 25 percent of the weight of theperfume composition. Excellent odorant results are obtained when theolfactory effective amount is up to about 5 percent on the same basis.For example, in bubble bath, the o1- factory amount of ethyl2,4-dioxohexanoate is suitably about 8 percent by weight. A preferredembodiment utilizes about 5 percent of the olfactory ingredient.

Where used as a flavoring ingredient, ethyl 2,4- dioxohexanoate isuseful for blending with food products to provide compositions having ataste characterized as: apple, butterscotch, butter-nut, maple andmaple-honey. Such flavors are of particular advantage in compositionssuch as confections, jams, jellies, syrups, ice cream and the like. Suchcompositions can contain, as the flavoring ingredient,ethyl2,4-dioxohexanoate alone or in an admixture with other flavoringingredients. For example, the dioxohexanoate compound can be mixed withvanillin, solid extract Foenugreek, etc., to produce a syrup which hasan imitation maple flavormg.

In using ethyl 2,4-dioxohexanoate as a synthetic flavoring, an effectiveamount of the flavoring compound is added to a food carrier to impart apalatable flavor. The relative amount of the flavoring compound in themixture (flavoring compound-i-food carrier) can be expressed as apercentage of the finished food product. The percentage varies interalia with the particular kind of food product, taste, etc.

Ethyl 2,4-dioxohexanoate can be incorporated into many food carriers,e.g., ice cream, custard, ice milk,

water ices, candy, flavor bases, cake mixes, icings, fill ings, and thelike.

1 Food palatable results are obtained when the effective amount of theflavoring compound constitutes up to about 5 percent of the weight ofthe food product. Excellent palatable results are obtained when theeffective amount of the flavoring compound constitutes up to about 1percent on the same basis As noted, the flavoring compound can be usedto produce other tasty food products such as table syrup, cream centercandy and the like. Where the flavoring compound is utilized in a tablesyrup, the effective amount of the flavoring compound constitutes fromabout 0.1 to about 0.5 percent of the weight of the food product.Likewise, cream center candy and ice cream suitably use from about 0.5percent of the weight of the food product. Likewise, cream center candyand ice cream suitably use from about 0.25 to about 1 percent of theflavoring compound on the same basis.

The olfactory ingredient and flavoring compound, namely, ethyl2,4-dioxohexanoate, can be prepared by a Claisen condensation of2-butanone and diethyl oxalate using a solution of sodium ethoxide inethyl alcohol as the base. Preferably, the ethyl alcohol is anhydrousand has a moisture content of less then 0.15 percent (by Karl Fischerdetermination) so as to produce good yields.

Ethyl 2,4-dioxohexanoate has already been described in the literature,for example, in 1906 by Otto Diels in Chem.Berichte 39, 1333. However,despite the fact that ethyl 2,4-dioxohexanoate has been known for overhalf a century, no one until now has recognized the unique olfactory andflavoring properties of this compound. It was accordingly mostsurprising to find that the fragrance of ethyl 2,4-dioxohexanoateprovides not only a desirable perfume odor, but also that the compoundpossesses the aforementioned desirable flavoring properties.

In order to illustrate our invention the following examples are giveneach of which utilizes ethyl 2,4- dioxohexanoate.

Purity (V.P.C. analysis) Empirical formula percent=9 l 98 a 12 4 EXAMPLE1 Preparation of ethyl 2,4-dioxohexanoate 236 gm of anhydrous ethylalcohol is distilled directly into a 1,000 ml three-necked flaskequipped with a fast agitator, water-cooled condenser, addition funnel,thermometer and gas-inlet/outlet tube. The reaction is conducted under anitrogen atmosphere. Anhydrous sodium ethoxide (68 gm) is added withagitation and the mixture refluxed for 1 hour. The mixture is thencooled to a range of 0 to 5C whereupon a mixture of 72 gm of 2-butanoneand 146 gm of diethyl oxalate is slowly added through the additionfunnel over a 30 minute period and under a nitrogen atmosphere at 0 to5C. The resulting mixture was then further cooled and agitated for 3hours at 0 to 5C.

After cooling to 0C, 168 ml of a 1:1 hydrochloric acid/H O (6M) solutionwas added and the temperature of the resultant solution was maintainedbelow 10C. The acidified solution was extracted twice, each time with300 ml of toluene. The organic phase was then successively washed twicewith 600 ml water, once with 600 ml of a 10 percent Na CO solution andonce with 400 ml of a saturated sodium chloride solution. The toluenelayers were then separated from the aqueous layers, combined, dried overmagnesium sulfate and filtered. The toluene was removed by distillationunder 25 mm/Hg pressure yielding ethyl 2,4-

dioxohexanoate. Purity (V.P.C.) about 91 percent. Optional and furtherpurification was effected by fractional distillation through a 6 inchglass Helix packed column at 0.2 mm/Hg. Distillation yielded:

Fract. Vapor Pot. Pressure l. -85C 958-104C 2.0 mm 2. C 104C 2.0 mm 3.86C 112C 2.0 mm 4. 89C 122C 2.0 mm 5. 85C 165C 2.0 mm

Vapor phase chromatography (V.P.C.) analysis (C/SE 30) showed Fract. lto be the desired product plus a small amount of unreacted diethyloxalate. Fracts. 2-4 were shown to be 97 99 percent of the desiredproduct and were accordingly combined to give a fraction of about 98percent pure ethyl 2,4- dioxohexanoate. Fract. 5 was shown to containthe desired product plus about 5 6 percent of unknown byproduct.

EXAMPLE 2 Preparation of Imitation Maple Flavoring An imitation maplesyrup containing the following ingredients Ingredients Amount methylcyclopentenolene l5 g vanillin 50 g gum balsam peru 5 g alcohol 190 375ml solid extract Foenugreek I25 g .caramel coloring 185 g ethyl2,4-dioxohexanoate 40 g water q.s.

L000 ml was prepared by:

l. combining the first seven ingredients above, and 2. bringing thesolution up to a final volume of 1,000 ml. with water (q.s.).

EXAMPLE 3 Preparation of Cassia Absolute Perfume Composition A perfumecomposition containing the following ingredients and having a Cassiaabsolute odor Ingredients Amount n-nonyl aldehyde 560 ml methyl n-nonylacetaldehyde 392 ml anisic aldehyde 280 ml anisyl aldehyde 280 ml benzylalcohol (P.G.)" 2240 ml citronellol extra I68 ml cuminic aldehyde 56 mldipropylene glycol I48 ml methyl Z-octynoate 560 ml geraniol 560 mlgeranyl butyrate 392 ml ethyl 2,4-dioxohexanoate 500 mlbenzopyrrole(indol) l0% in triethanolaminc 280 ml 2-nonenal pure 1% 112ml beta-iononc 560 ml hydroxycitronellal l I20 ml linalool coeur 280 mlmethyl salicylate(syn) 560 ml p-methyl acetophenone, 10% H2 ml styraxsoluble resin 560 ml terpineol extra 280 ml P.G. perfume grade wasprepared (10,000 ml) by:

l. combining the ingredients in the order as above listed, and

2. adequately mixing each ingredient into the resulting mixture in orderto ensure a homogenous dispersion of each ingredient.

EXAMPLE 4 Preparation of Tuberose Absolute Perfume Composition A perfumecomposition containing the following ingredients and having a Tuberoseabsolute odor Ingredients Amount methyl n-nonyl acetaldehyde 70 mlgamma-nonalactone 420 ml amyl cinnamic aldehyde 280 ml Aurantiol 57-20ml balsam tolu soluble resin 70 ml benzoin siam soluble resin 70 mlbenzyl acetate 700 ml benzyl salicylate 700 ml celery seed oil 70 mlfolione 70 ml ethyl 2,4-dioxohexanoate, 10% 500 ml indolene, 10% 42 mliso eugcnol extra I54 ml methyl benzoate 350 ml methyl salicylate (syn)364 ml methyl tuberate 28 ml vanilla soluble odo resin 42 ml Ylangbourbon extra 350 ml MethylN-3,7-dimethyl-7-hydroxyoctyliden-anthranilate was prepared (10,000 ml)by:

l. combining the ingredients in the order as above listed, and

2. adequately mixing each ingredient into the resulting mixture in orderto ensure a homogenous dispersion of each ingredient.

EXAMPLE 5 Preparation of Genet Absolute Perfume Composition A perfumecomposition containing the following ingredients and having a Genetabsolute odor Ingredients Amount benzo pyrone (coumarin) extra 16 mloranger crystals ethyl B-napthyl I 1 ml ketone lauryl acetate I mln-nonyl aldehyde, l0% in I 1 ml dipropylene glycol n-decyl aldehyde l lml n-decyl alcohol 3 ml Anisic Aldehyde 5 ml Aurantiol 50 3 ml BenzylAlcohol R0. 415 ml Constituant I5 29 ml P-cuminic aldehyde, l0% in 5 mldipropylene glycol ethyl phenyl acetate 5 ml ethyl propionate 5 mlfolione l% in dipropylene glycol 5 ml geraniol 3 ml ethyl2,4-dioxohexanoate I0 ml indol 10 ml iso eugenol 52 ml Labdanum solubleresin 52 ml Iaurine extra 52 ml linalyl acetate coeur 6 ml linalylphenyl acetate 52 ml methyl aceto phenone 10 ml Peru balsam solubleresin 124 ml phenyl ethyl alcohol extra 2l ml vetivert (El) 83 mlPerfume grade was prepared (1,000 ml) by:

l. combining the ingredients in the order as above listed, and

2. adequately mixing each ingredient into the resulting mixture in orderto ensure a homogenous dispersion of each ingredient.

EXAMPLE 6 Preparation of Scented Bar Soap A scented bar soap compositionis produced by incorporating the perfume composition prepared in Example5 into soap chips in the following manner so that the finished productcontains about I percent, by weight, of said perfume composition:

I. weigh soap chips and transfer into mixing container (percent ofperfume composition is based on total weight of chips used),

2. weigh perfume composition and premix with a small amount of soapchips,

3. combine premix with chips in container and mix until homogeneous,

4. pass chips through a worm-screw driver,

5. place ground chips into a die press and compress to a pressure ofabout 6,000 PSI, and

6. remove compressed cake and 'cut into quarters.

EXAMPLE 7 Preparation of Scented Bath Salts A scented bath saltscomposition is produced by incorporating ethyl 2,4-dioxohexanoate intothe-following ingredients in the following manner so that the finishedcomposition contains about percent, by weight, of the dioxohexanoatecompound:

Ingredients Amount sodium sesquicarbonate 90 magnesium carbonate 5 ethyl2,4-dioxohexanoate 5 was prepared by:

1. grinding the ethyl 2,4-dioxohexanoate into the magnesium carbonate ina milling apparatus,

2. adding the perfumed magnesium carbonate to the position is a bathsalt.

2. The method of claim 1 wherein the said cosmetic composition is aperfume containing a mixture of different perfume ingredients other thanethyl 2,4-dioxohexanoate.
 3. The method of claim 1 wherein said cosmeticcomposition is a bath salt.